Anthracene dyes and process of making same.



UNITED STATES PATENT oFFIcE;

MAX HENRY ISLER, OIYILNNHE II, GERMANY, ASSIGNOR '10 BADISGHE ANILIN 8nSODA FABRIK, OF LUDWIGmmNPONT-THE BHINE, GERMANY, A CORPORATION.

No Drawing.

Specification of Letters Iatent. I AppHoatIon filed September 8, 1911.Serial Ro..647,932.

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To all whom it may concern:

Be it known that I, Max I'IENRY Isnnn, citizen of the Swiss Republic,residing atfMannheim, Germany, have invented new and useful ImprovementsinAnthracene Dyes and Processes of Making Same, of which the followingis a specification.

My invention consists in the roduction of a new class of anthraquinoneerivatives which I regard as hydrazones of the anthraquinone series.These new compounds can be obtained by treating an anthraquinonealdehyde, or a derivatlve thereof, with a hydrazin bf the anthraquinoneseries. Instead of employin' the anthraquinone' aldehydes themselves,tie corresponding omega-dihalogen methyl-anthraquinone compounds can beemployed, as they give rise tothe same products and can thereforeberegarded as equivalent to the aldehydes. 'I prefer to carry out thereaction by treating the an-' thraquinone aldehyde, orderivativethereof,

with the hydrazin with, or without, the use of a solvent or a diluent,and the reaction generally takes placesvery rapidly, g'ivm' g= rise tovcompounds which are either-themselves colorin matters 'or which can beused in the manu acture of coloring mattersl The hydrazine ,of theanthraquinone series which are employed according to my invention can beobtained, for instance, as described in German Patent No. 163,447.

The following examples will serve to illustrate how this mv-ention canbe carried into 5 practical effect, but my invention is not limitedtothese examples. The parts are .by weight.

Example 1: Boil together for fifteen minutes, fourteen parts ofl-chlor-anthraqui- J none-2-aldehyde, twelve parts ofanthraquinone-2hydrazin, and three hundred parts of naphthalene. Afterthe reaction is complete, remove the naphthalene, for instance by meansof toluene, wherepipqn the desired 5 product is obtained as are powderwhich yields a bluish red solution in concentrated sulfuric acid. Itdyes cotton, from a vat, deep Bordeaux red shades.

The product is probably a hydrazone possesslng aconstitutioncorresponding to the formula r o omegad1chlo1-2-methyl-anthraquinone,thirit 65 teen parts ofanthraquinone-2-hydrazin, ten parts of anhydrous sodium acetate, and twohundred partsof' nitrobenzene. When, from a test portion, it is seenthat the formation of the coloring matter is complete, allow the mass tocool to about fift degrees centigrade oring matter is like that obtainedfrom an.- thra uinoneQ-aldehyde and fillthlfltlllllOIlB- Q-hy azin, asdescribed in the foregoing example.'

Example 3: Treat sixteen parts of l-hydroxy 4 brom 'anthraquinone2-aldehyde,

twelve parts of anthraquinone-2-hydrazin, and three hundred parts ofnaphthalene in a manner similar to t at described in the foregoinExample L From the vat the prod:

uct o tained dyes cotton violet.

Example 4: Gondense fifty-fiveparts of l chlor-anthra uinone-2-aldehydeand twentyseven parts 0 anthraquinone-Lfi-dihydrazin, the mannerdescribed in the foregoing Example 1;- The product yields a yellow-redsolution in concentrated sulfuric acid and it is almost insoluble inboiling nitrobenzene. It dyes'cotton, from the hydrosulfite vat,

Bordeaux red. If, in this example, the anthraquinone-l.5-dihydrazin .bereplaced by anthraquinone-2.6-dihydrazin, a somewhat yellower coloringmatter is obtained. Example 5: Treat thirteen parts of nitro-'anthraquinone-2-aldehyde (obtainable by ni- Patented Dec. 1'7, 1912.

70 and filter, and wash wit alcohol. The coltratinganthraquinone-2-aldehyde), twenty- I four parts ofanthraquinone-Q-hydrazin, and l three hundred parts of naphthalene inthe manner described in the foregoing Example 1. The product yields abeautiful carmine red solution in concentrated sulfuric acid and dyescotton pure Bordeaux red. The analogous coloring matter can be obtainedfrom the amino compound produced by reducing the aforesaidnitro-anthraquinone-2- aldehyde. In this example, instead ofanthraquinone-Q-hydrazin, anthraquinone-1.5- dihydrazin, oranthraquinone-2.6-dihydrazin, or a derivative thereof or of.otheranthraquinone-lnonoor di-hydrazins can be employed.

The following table gives some of the properties of a few of thecoloring matters obtainable according to my invention Condensationproduct- Solution intti itti From- Andgg gi ggi fi? +Borlc acid.

Anthraquinone-Z-aldehyde Anthraquinone-ahydrazin Dull red Cherry redUnchanged.

1chlor-anthraquinone-2aldehyde .do .do Blulsh red Do.

1-hydroxy-4-brom-anthraquinone-2-al- .....do Dullviolet do Do.

dehyde.

1-hydroxy-anthraquinone-Z-aldehyde. .do .do .do Do.

fi-chlor-anthraquinone-2-aldehyde .do Dull red Cherry red D0.

1.fi-dichlor-anthraquinone-%aldehyde .do Yellowlsh red.. do D0.4-chlor-anthmquinone-l-aldehyde Anthraquinone-2-hydrazin Brick redBlulsh red I Do.

Do Anthraquinone-l-hydrazln Yellow-red..... Brown-yellow.. Cherry red.

Anthraqulnone-2-aldehyde ..do Dull red Yellow-red.-. Cherry red.Ilitro-anthraquinone-2-aldehyde Anthraquinone-Zhydremin Pure Bordeaux.Carmine red.... Unchanged.

Amino-anthraquinone-2-aldehyde .do Dull red Cherry red Do.

l-chlor-anthraquinone-2-aldehyde Anthraquin'one-l.t'rdihydrazin DullBordeaux Yel1ow-red..... Green-blue.

The 4 chlor --anthraquinone 1 aldehyde mentioned above can be obtainedby condensing phthalic anhydrid with para-chlortoluene and thenchlorinating the l-methyll-chlor-anthraquinone thus obtained, so thattwo atoms of chlorin enter the methyl group, and then subjecting theproduct obtained to saponification.

Now what I claim is:

LThB process of producing coloring matter ofthe anthracene series bytreating an anthraquinone aldehyde with a hydrazin of. the anthraceneseries.

2. The process of producing coloring matter of the anthracene series bytreating 1- chlor-anthraquinone-Q-aldehyde with anthraquinone2-hydrazin.

3. As new articles of manufacture the coloring matters which can beobtained by treating an anthraquinone aldehyde with a hydra'zin of theanthracene series, Which and consists when dry of a red powder,

yields a bluish red solution in ooneenti'avted my hand in the presenceof two subscribing sulfuric acid. which solution is unchanged witnesses.

-in (0101' on the addition of boric acid and MAX HENRY ISLER.-

\Yilil'il dyes vollou from an alkaline hydro- \Vitnesses: sul'fitu vatdull violet shades. J. ALEC. LLOYD, I

In testimony whereof I have hereunto set Josm'n HEIFFER.

